Photographic products and processes employing nondiffusible 1-arylazo-4-isoquinolinol dye-releasing compounds

ABSTRACT

Photographic elements, diffusion transfer assemblages and processes are described which employ a novel nondiffusible compound having a releasable 1-arylazo-4-isoquinolinol dye moiety. The compound contains: 
     (a) in the ortho position of the arylazo moiety a metal chelating group, a salt thereof or a hydrolyzable precursor thereof; and 
     (b) a ballasted carrier moiety which is capable of releasing the diffusible azo dye under alkaline conditions. The dye is transferred imagewise to an image-receiving layer where it is contacted with metal ions to form a metal-complexed azo dye transfer image of excellent stability.

This invention relates to photography and more particularly to colordiffusion transfer photography employing certain nondiffusible azodye-releasing compounds which, as a function of development of a silverhalide emulsion layer, release a diffusible, metallizable1-arylazo-4-isoquinolinol dye. Highly stable metal complexes of this dyeare formed in an image-receiving layer.

Azo dye developers containing metallizable groups are disclosed in U.S.Pat. Nos. 3,081,167; 3,196,014; 3,299,041; 3,453,107; 3,563,739;3,544,545 and 3,551,406. Since it is a reactive species, however, thedeveloper moiety of such dye developers is capable of developing anyexposed silver halide emulsion layer with which it comes into contact,rather than just developing the adjacent silver halide emulsion withwhich it is associated. Unwanted wrong-layer development, therefore, canoccur in dye developer systems which results in undesirable interimageeffects. Accordingly, it is desirable to provide an improved transfersystem in which the dye is not attached to a "reactive" moiety, such asa developer moiety, so that such dye can diffuse throughout thephotographic film unit without becoming immobilized in undesired areas.

In U.S. Published Patent Application B351,673, published Jan. 28, 1975,nondiffusible dye releasing compounds are disclosed. Among the variousdye moieties disclosed which can be released are "metal complexed dyes".No specific structures are shown, however.

Andronova et al, Isvestiya Akad. Nauk SSSR, Ser. Khim., Trans. Ed. 452(1972) describe the synthesis of a few simple1-arylazo-4-isoquinolinols. The compounds employed in the instantinvention and their use in photographic products are not shown, however.

In U.S. Pat. Nos. 3,931,144; 3,932,380; 3,942,987; 3,954,476; 4,001,209;4,013,633 and 4,013,635, various nondiffusible azo dye-releasingcompounds are disclosed. The released dyes, however, are not disclosedas being metallized or metallizable.

The April 1977 edition of Research Disclosure, pages 32 through 39,discloses various nondiffusible dye-releasing compounds and variousmetallized azo dye fragments. Such premetallized dyes are largemolecules which diffuse more slowly than unmetallized dyes, resulting inlong access times for image formation in color image transfer systems.The specific compounds employed in the instant invention, however, arenot disclosed.

U.S. Pat. Nos. 2,864,813; 3,086,005; 3,492,287 and 3,985,499 disclosevarious azo dyes, U.S. Pat. Nos. 2,348,417; 2,495,244; and 2,830,042 andFrench Pat. Nos. 1,124,882 and 1,200,358 disclose various dyes fromazopyridines, while U.S. Pat. Nos. 2,868,775; 2,938,895; 3,097,196;3,691,161; and 3,875,139; British Patent 899,758; French Patent1,129,702 and an article entitled "The Irgalan Dyes -- Neutral-DyeingMetal-Complex Dyes" by Guido Schetty, J. Soc. Dyers and Colourists,Volume 71, 1955, pages 705 through 724, disclose various metal complexeddyes. Again, however, neither the specific compounds employed in theinstant invention nor the results obtained therewith are disclosed.

In commonly assigned copending U.S. application Ser. No. 822,188 ofBaigrie et al, filed Aug. 5, 1977, there is a generic description ofmetallizable compounds which would encompass those of the instantinvention. The compounds of the instant invention are not specificallytaught by Baigrie et al, however, and the results obtained with theinstant invention are unexpectedly superior, as described below.

It would be desirable to provide improved dye-releasing compoundscontaining chelating dye moieties, so that the dye which is releasedimagewise during processing can diffuse to an image-receiving layercontaining metal ions to form a metal-complexed, dye transfer imagehaving better hues, rapid diffusion rates and shorter access times thanthose of the prior art, as well as good stability to heat, light andchemical reagents. Many of the dyes of the present invention, whenchelated by metal ions such as nickel(II) ions, have good cyan hue withminimal unwanted absorption outside the red region of the spectrum. Theyhave superior stability to fading by light in a variety of environments.In addition, the cyan hue is obtained without having a nitro group onthe ring which is the case with most cyan dyes. In a strong reducingenvironment, nitro groups tend to be reduced, thereby destroying thecyan hue. The absence of such a nitro group is, therefore, advantageous.

A photographic element in accordance with the invention comprises asupport having thereon at least one photosensitive silver halideemulsion layer having associated therewith a nondiffusible compoundhaving at least one diffusible 1-arylazo-4-isoquinolinol dye moiety,said compound containing:

(a) in the ortho position of the arylazo moiety a metal chelating group,a salt thereof or a hydrolyzable precursor thereof; and

(b) a ballasted carrier moiety which is capable of releasing saiddiffusible azo dye under alkaline conditions, such as, for example, as afunction (either direct or inverse) of development of the silver halideemulsion layer.

Good cyan dyes may be obtained in a preferred embodiment of theinvention when the 1-arylazo-4-isoquinolinol dye releasing compound isrepresented by the formula: ##STR1## wherein:

G is a metal chelating group (any group which will donate a pair ofelectrons to a metal ion), a salt thereof (such as an alkali metal salt,a quaternary ammonium salt, etc) or a hydrolyzable precursor thereof(e.g., a hydrolyzable acyl or ester group); a group which together with##STR2## is CAR, said CAR being bonded to the benzene ring through theoxygen of said ##STR3## or a group which together with SO₂ NH is CAR,and CAR being bonded to the benzene ring through the SO₂ NH group(either --SO₂ NH or --NHSO₂ being bonded directly to the benzene ring);

G¹ is a hydroxy group or a salt thereof (such as a sodium salt, atetramethylammonium salt, etc,) or a hydrolyzable precursor thereof or agroup which together with ##STR4## is CAR which is bonded to theisoquinoline ring through the oxygen of the ##STR5## (the oxygen beingbonded directly to the isoquinoline ring);

CAR represents a ballasted carrier moiety; and

t is an integer of 0 or 1, with the proviso that the compound containsat least one but not more than two CAR groups.

For example, G may be hydroxy; amino; carboxy; sulfonamido; sulfamoyl; afused nitrogen-containing ring; or a hydrolyzable ester group having theformula --OCOR¹, --OCOOR¹, or --COOR¹, wherein R¹ is an alkyl grouphaving 1 to about 8 carbon atoms, such as methyl, ethyl, isopropyl,butyl and the like, or an aryl group having 6 to about 12 carbon atoms,such as phenyl, etc.

Examples of hydrolyzable precursors of a hydroxy group for G¹ include,for example, an acyloxy group having the formula --OCOR¹, --OCOOR¹ or--OCON(R¹)₂, wherein each R¹ is an alkyl group having 1 to about 8carbon atoms, such as methyl, ethyl, isopropyl, butyl and the like, oran aryl group having 6 to about 12 carbon atoms, such as phenyl, etc.

In a preferred embodiment of the invention, t is l, G is OH, G¹ is OHand CAR is attached to the benzene ring, rather than being attached tothe isoquinoline ring. Other substituents may also be present in eitherof the two rings, such as alkyl of 1 to 6 carbon atoms, alkoxy, amino,halogens, acetamido, carbamoyl, alkoxycarbonyl, solubilizing groups suchas sulfonamido, sulfamoyl, carboxy, sulfo, hydrolyzable precursorsthereof, etc. In a preferred embodiment, the isoquinoline ring issubstituted in the 3-position with a methyl group.

In another preferred embodiment of the invention, CAR may have attachedthereto two azo dye moieties of the formula above, in which case two dyemoieties will be released from one CAR moiety.

When hydrolyzable precursors for G and G¹ of the dye moiety in the aboveformula are employed, the absorption spectrum of the azo dye is shiftedto shorter wavelengths. "Shifted dyes" of this type absorb light outsidethe range to which the associated silver halide layer is sensitive. Insome cases, the absorption spectrum of the unmetallized azo dye ligandis substantially shifted to shorter wavelengths at neutral pH (e.g., 5to 8).

There is great latitude in selecting a CAR moiety which is attached tothe 1-arylazo-4-isoquinolinol dye-releasing compounds described above.Depending upon the nature of the ballasted carrier selected, variousgroups may be needed to attach or link the carrier moiety to the dye.Such linking groups are considered to be a part of the CAR moiety in theabove definition. It should also be noted that when the dye moiety isreleased from the compound, cleavage may take place in such a positionthat part or all of the linking group, if one is present, and even partof the ballasted moiety may be transferred to the image-receiving layeralong with the dye moiety. In any event, the dye nucleus as shown abovecan be thought of as the "minimum" which is transferred.

CAR moieties useful in the invention are described in U.S. Pat. Nos.3,227,550; 3,628,952; 3,227,552; and 3,844,785 (dye released bychromogenic coupling); U.S. Pat. Nos. 3,443,939 and 3,443,940 (dyereleased by intramolecular ring closure); U.S. Pat. Nos. 3,698,897 and3,725,062 (dye released from hydroquinone derivatives); U.S. Pat. No.3,728,113 (dye released from a hydroquinonylmethyl quaternary salt);U.S. Pat. Nos. 3,719,489 and 3,443,941 (silver ion induced dye release);and U.S. Pat. Nos. 3,245,789 and 3,980,497; Canadian Pat. No. 602,607;British Pat. No. 1,464,104; Research Disclosure 14447, April 1976; andcommonly assigned copending U.S. application Ser. No. 775,025, filedMar. 7, 1977 of Chasman et al (dye released by miscellaneousmechanisms), the disclosures of which are hereby incorporated byreference.

In a further preferred embodiment of the invention, the ballastedcarrier moiety or CAR, as described above, may be represented by thefollowing formula:

    (Ballast-Carrier-Link) --

wherein:

(a) Ballast is an organic ballasting radical of such molecular size andconfiguration as to render the compound nondiffusible in a photographicelement during development in an alkaline processing composition;

(b) Carrier is an oxidizable acyclic, carbocyclic or heterocyclic moiety(see "The Theory of the Photographic Process", by C. E. K. Mees and T.H. James, Third Edition, 1966, pages 282 to 283), e.g., moietiescontaining atoms according to the following configuration:

    a (--C═C).sub.b --

wherein:

b is a positive integer of 1 to 2; and

a represents the radicals OH, SH, NH--, or hydrolyzable precursorsthereof; and

(c) Link represents a group which, upon oxidation of said Carriermoiety, is capable of being hydrolytically cleaved to release thediffusible azo dye. For example, Link may be the following groups:##STR6## wherein * represents the position of attachment to the Carrier.

The Ballast group in the above formula is not critical as long as itconfers nondiffusibility to the compound. Typical Ballast groups includelong-chain alkyl radicals linked directly or indirectly to the compoundas well as aromatic radicals of the benzene and naphthalene seriesindirectly attached or fused directly to the ring, etc. Useful Ballastgroups generally have at least 8 carbon atoms such as substituted orunsubstituted alkyl groups of 8 to 22 carbon atoms, a carbamoyl radicalhaving 8 to 30 carbon atoms such as --CONH(CH₂)₄ --O--C₆ H₃ (C₅ H₁₁)₂,--CON(C₁₂ H₂₅)₂, etc, a keto radical having 8 to 30 carbon atoms such as--CO--C₁₇ H₃₅, --CO--C₆ H₄ (t--C₁₂ H₂₅), etc.

For specific examples of Ballast-Carrier-Link moieties useful as the CARmoiety in this invention, reference is made to the November 1976 editionof Research Disclosure, pages 68 through 74, and the April 1977 editionof Research Disclosure, pages 32 through 39, the disclosures of whichare hereby incorporated by reference.

In a highly preferred embodiment of the invention, the ballasted carriermoiety or CAR in the above formulas is a group having the formula:##STR7## wherein:

(a) Ballast is an organic ballasting radical of such molecular size andconfiguration (e.g., simple organic groups or polymeric groups) as torender the compound nondiffusible in a photographic element duringdevelopment in an alkaline processing composition;

(b) D is OR² or NHR³ wherein R² is hydrogen or a hydrolyzable moiety andR³ is hydrogen or a substituted or unsubstituted alkyl group of 1 to 22carbon atoms such as methyl, ethyl, hydroxyethyl, propyl, butyl,secondary butyl, tert-butyl, cyclopropyl, 4-chlorobutyl, cyclobutyl,4-nitroamyl, hexyl, cyclohexyl, octyl, decyl, octadecyl, dodecyl,benzyl, phenethyl, etc. (when R³ is an alkyl group of greater than 8carbon atoms, it can serve as a partial or sole Ballast);

(c) Y represents the atoms necessary to complete a benzene nucleus, anaphthalene nucleus, or a 5 to 7 membered heterocyclic ring such aspyrazolone, pyrimidine, etc;

(d) j is a positive integer of 1 to 2 and is 2 when D is OR² or NHR³when R³ is hydrogen or an alkyl group of less than 8 carbon atoms; and

(e) L is a linking group which is [X--(NR⁴ --J)_(q) ]_(m) -- orX--J--NR⁴ -- wherein:

(i) X represents a bivalent linking group of the formula --R⁵ --L'_(n)--R⁵ _(p) -- where each R⁵ can be the same or different and eachrepresents an alkylene radical having 1 to about 8 carbon atoms, such asmethylene, hexylene and the like; a phenylene radical; or a substitutedphenylene radical having 6 to about 9 carbon atoms, such as methoxyphenylene;

(ii) L' represents a bivalent radical selected from oxy, imino,carbonyl, carboxamido, carbamoyl, sulfonamido, ureylene, sulfamoyl,sulfinyl or sulfonyl;

(iii) n is an integer of 0 or 1;

(iv) p is 1 when n equals 1 and p is 1 or 0 when n equals 0, providedthat when p is 1 the carbon content of the sum of both R⁵ radicals doesnot exceed 14 carbon atoms;

(v) R⁴ represents a hydrogen atom, or an alkyl radical having 1 to about6 carbon atoms;

(vi) J represents a bivalent radical selected from sulfonyl or carbonyl;

(vii) q represents an integer of 0 or 1; and

(viii) m represents an integer of 0, 1 or 2.

Especially good results are obtained in the above formula when D is OH,j is 2, and Y is a naphthalene nucleus.

Examples of the CAR moiety in this highly preferred embodiment aredisclosed in U.S. Published Patent Application B351,673; U.S. Pat. No.3,928,312; French Pat. No. 2,284,140; and German Pat. Nos. 2,406,664;2,613,005; and 2,505,248, the disclosures of which are herebyincorporated by reference, and include the following: ##STR8##

In another highly preferred embodiment of the invention, the ballastedcarrier moiety or CAR in the above formulas is such that the diffusibleazo dye is released as an inverse function of development of the silverhalide emulsion layer under alkaline conditions. This is ordinarilyreferred to as positive-working dye-release chemistry. In one of theseembodiments, the ballasted carrier moiety or CAR in the above formulasmay be a group having the formula: ##STR9## wherein:

Ballast is an organic ballasting radical of such molecular size andconfiguration as to render the compound nondiffusible in a photographicelement during development in an alkaline processing composition;

W² represents at least the atoms necessary to complete a benzene nucleus(including various substituents thereon); and

R⁷ is an alkyl (including substituted alkyl) radical having 1 to about 4carbon atoms.

Examples of the CAR moiety in this formula I include the following:##STR10##

In a second embodiment of positive-working dye-release chemistry asreferred to above, the ballasted carrier moiety or CAR in the aboveformulas may be a group having the formula: ##STR11## wherein:

Ballast is an organic ballasting radical of such molecular size andconfiguration as to render the compound nondiffusible in a photographicelement during development in an alkaline processing composition;

W¹ represents at least the atoms necessary to complete a quinone nucleus(including various substituents thereon);

r is a positive integer of 1 or 2;

R⁶ is an alkyl (including substituted alkyl) radical having 1 to about40 carbon atoms or an aryl (including substituted aryl) radical having 6to about 40 carbon atoms; and

k is a positive integer of 1 to 2 and is 2 when R⁶ is a radical of lessthan 8 carbon atoms.

Examples of the CAR moiety in this formula II include the following:##STR12##

In using the compounds in formulas I and II above, they are employed ina photographic element similar to the other nondiffusible dye-releasersdescribed previously. Upon reduction of the compound as a function ofsilver halide development under alkaline conditions, the metallizableazo dye is released. In this embodiment, conventional negative-workingsilver halide emulsions, as well as direct-positive emulsions, can beemployed. For further details concerning these particular CAR moieties,including synthesis details, reference is made to commonly assignedcopending U.S. Application Ser. No. 775,025 of Chasman et al, filed Mar.7, 1977, the disclosure of which is hereby incorporated by reference.

In a third embodiment of positive-working dye-release chemistry asreferred to above, the ballasted carrier moiety or CAR in the aboveformulas may be a group having the formula: ##STR13## wherein:

Ballast, W² and R⁷ are as defined for formula I above.

Examples of the CAR moiety in this formula III include the following:##STR14##

For further details concerning this particular CAR moiety, includingsynthesis details, reference is made to commonly assigned copending U.S.application Ser. No. 534,966 of Hinshaw et al, filed Dec. 20, 1974, thedisclosure of which is hereby incorporated by reference.

In a fourth embodiment of positive-working dye-release chemistry asreferred to above, the ballasted carrier moiety or CAR in the aboveformulas may be a group having the formula: ##STR15## wherein:

Ballast, r, R⁶ and k are as defined for formula II above;

W² is as defined for formula I above; and

K is OH or a hydrolyzable precursor thereof.

Examples of the CAR moiety in this formula IV include the following:##STR16##

For further details concerning this particular CAR moiety, includingsynthesis details, reference is made to U.S. Pat. No. 3,980,479 ofFields et al, issued Sept. 14, 1976, the disclosure of which is herebyincorporated by reference.

A bivalent linking group, e.g., L or X as defined above, may be used, ifdesired, to link the CAR moiety described in formulas I through IV aboveto the dye moiety previously described.

Other examples of CAR include the following: ##STR17##

Representative compounds included within the scope of the inventioninclude the following: ##STR18##

A process for producing a photographic transfer image in color accordingto the invention comprises:

(a) treating an imagewise-exposed photographic element, as describedabove, with an alkaline processing composition in the presence of asilver halide developing agent to effect development of each of theexposed silver halide emulsion layers;

(b) the dye-releasing compound then releasing the diffusible azo dye, asdescribed above, imagewise as a function of the development of each ofthe silver halide emulsion layers;

(c) at least a portion of the imagewise distribution of the azo dyediffusing to a dye image-receiving layer; and

(d) contacting the imagewise distribution of azo dye with metal ions,thereby forming a metal-complexed azo dye transfer image.

In another preferred embodiment of the invention, a process forproducing a photographic transfer image in color according to theinvention comprises:

(a) treating an imagewise-exposed photographic element as describedabove wherein CAR in the compound has the formula: ##STR19## D, Y, L andj being defined as above, with an alkaline processing composition in thepresence of a silver halide developing agent to effect development ofeach of the exposed silver halide emulsion layers, thereby oxidizing thedeveloping agent;

(b) the oxidized developing agent thereby cross-oxidizing thedye-releasing compound;

(c) the cross-oxidized dye-releasing compound then cleaving as a resultof alkaline hydrolysis to release the diffusible azo dye imagewise as afunction of the imagewise exposure of each of the silver halide emulsionlayers;

(d) at least a portion of the imagewise distribution of the azo dyediffusing to a dye image-receiving layer; and

(e) contacting the imagewise distribution of azo dye with metal ions,thereby forming a metal-complexed azo dye transfer image.

The tridentate azo dye ligand which is released from the dye-releasingcompounds in accordance with the present invention will form acoordination complex in the image-receiving layer with polyvalent metalions. The metal ions can be present in the image-receiving layer itselfor in a layer adjacent thereto, or the image-receiving layer can becontacted with metal ions in a bath after diffusion of the dye has takenplace. Metal ions most useful in the invention are those which: areessentially colorless when incorporated into the image-receivingelement, are inert with respect to the silver halide layers, reactreadily with the released dye to form a complex of the desired hue, aretightly coordinated to the dye in the complex, have a stable oxidationstate, and form a dye complex which is stable to heat, light andchemical reagents. In general, good results are obtained with polyvalentmetal ions such as copper (II), zinc (II), nickel (II), platinum (II),palladium (II) and cobalt (II) ions.

It is believed that the coordination complex which is formed from thetridentate azo dye ligand according to the invention in one of thepreferred embodiments thereof has the following structure: ##STR20##where Me is metal and Lig is one or more ligand groups depending uponthe coordination number of the metal ion, such as H₂ O, Cl, pyridine,etc.

Thus, in accordance with another embodiment of the invention, aphotographic element is provided which comprises a support havingthereon a coordination complex of a polyvalent metal ion and a compoundhaving the formula: ##STR21## wherein G is a metal chelating group.

The element usually contains a photographic mordant or image-receivinglayer to bind the dye or coordination complex thereto. The structuresshown above may also, of course, be substituted in the same manner asdescribed above for the starting compounds from which they are released,e.g., the isoquinoline ring may be substituted in the 3-position with amethyl group, etc.

It will be appreciated that, after processing the photographic elementdescribed above, there remains in the element, after transfer has takenplace, an imagewise distribution of azo dye in addition to developedsilver. A color image comprising residual nondiffusible compound may beobtained in this element if the residual silver and silver halide areremoved by any conventional manner well known to those skilled in thephotographic art, such as a bleach bath followed by a fix bath, ableach-fix bath, etc. Such a retained dye image should normally betreated with metal ions to metallize the dyes to increase their lightfastness and shift their spectral absorption to the intended region. Theimagewise distribution of azo dye may also diffuse out of the elementinto these baths, if desired, rather than to an image-receiving element.If a negative-working silver halide emulsion is employed in certainpreferred photosensitive elements, described above, then a positivecolor image, such as a reflection print, a color transparency or amotion picture film, may be produced in this manner. If adirect-positive silver halide emulsion is employed in suchphotosensitive elements, then a negative color image may be produced.

The photographic element in the above-described process can be treatedwith an alkaline processing composition to effect or initiatedevelopment in any manner. A preferred method for applying processingcomposition is by use of a rupturable container or pod which containsthe composition. In general, the processing composition employed in thisinvention contains the developing agent for development, although thecomposition could also be solely an alkaline solution where thedeveloper is incorporated in the photographic element, theimage-receiving element or the process sheet, in which case the alkalinesolution serves to activate the incorporated developer.

A photographic film unit which can be processed in accordance with thisinvention is adapted to be processed by passing the unit between a pairof juxtaposed pressure-applying members, such as would be found in acamera designed for in-camera processing, and comprises:

(1) a photographic element as described above;

(2) a dye image-receiving layer; and

(3) an alkaline processing composition and means for discharging samewithin the film unit, such as a rupturable container which is adapted tobe positioned during processing of the film unit so that a compressiveforce applied to the container by the pressure-applying members willeffect a discharge of the container's contents within the film unit;

the film unit containing a silver halide developing agent.

In the embodiment described above, the dye image-receiving layer mayitself contain metal ions, or the metal ions may be present in anadjacent layer, so that the tridentate azo dye ligand which is releasedwill form a coordination complex therewith. The dye thus becomesimmobilized in the dye image-receiving layer and metallized at the sametime. Alternatively, the dye image in the dye image-receiving layer maybe treated with a solution containing metal ions to effectmetallization. The formation of the coordination complex shifts theabsorption of the dye to the desired hue, usually to longer wavelengths,which have a different absorption than that of the initial dye-releasingcompound. If this shift is large enough, then the dye-releasing compoundmay be incorporated in a silver halide emulsion layer without adverselyaffecting its sensitivity.

The dye image-receiving layer in the above-described film unit can belocated on a separate support adapted to be superposed on thephotographic element after exposure thereof. Such image-receivingelements are generally disclosed, for example, in U.S. Pat. No.3,362,819. When the means for discharging the processing composition isa rupturable container, it is usually positioned in relation to thephotographic element and the image-receiving element so that acompressive force applied to the container by pressure-applying members,such as would be found in a typical camera used for in-cameraprocessing, will effect a discharge of the container's contents betweenthe image-receiving element and the outermost layer of the photographicelement. After processing, the dye image-receiving element is separatedfrom the photographic element.

The dye image-receiving layer in the above-described film unit can alsobe located integral with the photographic element between the supportand the lowermost photosensitive silver halide emulsion layer. Oneuseful format for integral receiver-negative photographic elements isdisclosed in Belgian Pat. No. 757,960. In such an embodiment, thesupport for the photographic element is transparent and is coated withan image-receiving layer, a substantially opaque light-reflective layer,e.g., TiO₂, and then the photosensitive layer or layers described above.After exposure of the photographic element, a rupturable containercontaining an alkaline processing composition and an opaque processsheet are brought into superposed position. Pressure-applying members inthe camera rupture the container and spread processing composition overthe photographic element as the film unit is withdrawn from the camera.The processing composition develops each exposed silver halide emulsionlayer, and dye images, formed as a function of development, diffuse tothe image-receiving layer to provide a positive, right-reading imagewhich is viewed through the transparent support on the opaque reflectinglayer background. For other details concerning the format of thisparticular integral film unit, reference is made to the above-mentionedBelgian Pat. No. 757,960.

Another format for integral negative-receiver photographic elements inwhich the present invention can be employed is disclosed in Belgian Pat.No. 757,959. In this embodiment, the support for the photographicelement is transparent and is coated with the image-receiving layer, asubstantially opaque, light-reflective layer and the photosensitivelayer or layers described above. A rupturable container, containing analkaline processing composition and an opacifier, is positioned betweenthe top layer and a transparent cover sheet which has thereon aneutralizing layer and a timing layer. The film unit is placed in acamera, exposed through the transparent cover sheet and then passedthrough a pair of pressure-applying members in the camera as it is beingremoved therefrom. The pressure-applying members rupture the containerand spread processing composition and opacifier over the negativeportion of the film unit to render it light-insensitive. The processingcomposition develops each silver halide layer and dye images, formed asa result of development, diffuse to the image-receiving layer to providea positive, right-reading image which is viewed through the transparentsupport on the opaque reflecting layer background. For further detailsconcerning the format of this particular integral film unit, referenceis made to the above-mentioned Belgian Pat. No. 757,959.

Still other useful integral formats in which this invention can beemployed are described in U.S. Pat. Nos. 3,415,644; 3,415,645;3,415,646; 3,647,437; and 3,635,707. In most of these formats, aphotosensitive silver halide emulsion is coated on an opaque support,and a dye image-receiving layer is located on a separate transparentsupport superposed over the layer outermost from the opaque support. Inaddition, this transparent support also preferably contains aneutralizing layer and a timing layer underneath the dye image-receivinglayer.

Another embodiment of the invention uses the image-reversing techniquedisclosed in British Pat. No. 904,364, page 19, lines 1 through 41. Inthis process, the dye-releasing compounds are used in combination withphysical development nuclei in a nuclei layer contiguous to thephoto-sensitive silver halide negative emulsion layer. The film unitcontains a silver halide solvent, preferably in a rupturable containerwith the alkaline processing composition.

The film unit or assembly used in the present invention may be used toproduce positive images in single- or multicolors. In a three-colorsystem, each silver halide emulsion layer of the film assembly will haveassociated therewith a dye-releasing compound which releases a dyepossessing a predominant spectral absorption within the region of thevisible spectrum to which said silver halide emulsion is sensitive(initially or after forming the coordination complex), i.e., theblue-sensitive silver halide emulsion layer will have a yellow oryellow-forming dye-releaser associated therewith, the green-sensitivesilver halide emulsion layer will have a magenta or magenta-formingdye-releaser associated therewith, and the red-sensitive silver halideemulsion layer will have a cyan or cyan-forming dye-releaser associatedtherewith, at least one of the dye-releasers being a compound inaccordance with the present invention. The dye-releaser associated witheach silver halide emulsion layer may be contained either in the silverhalide emulsion layer itself or in a layer contiguous to the silverhalide emulsion layer.

The concentration of the dye-releasing compounds that are employed inthe present invention may be varied over a wide range, depending uponthe particular compound employed and the results desired. For example,the dye-releasers of the present invention may be coated in layers byusing coating solutions containing between about 0.5 and about 8 percentby weight of the dye-releaser distributed in a hydrophilic film-formingnatural material or synthetic polymer, such as gelatin, polyvinylalcohol, etc, which is adapted to be permeated by aqueous alkalineprocessing composition.

Depending upon which CAR is used in the present invention, a variety ofsilver halide developing agents can be employed. In certain embodimentsof the invention, any silver halide developing agent can be employed aslong as it cross-oxidizes with the dye-releasers described herein. Thedeveloper may be employed in the photosensitive element to be activatedby the alkaline processing composition. Specific examples of developerswhich can be employed in this invention include:

N-methylaminophenol

Phenidone (1-phenyl-3-pyrazolidone)

Dimezone (1-phenyl-4,4-dimethyl-3-pyrazolidone) aminophenols

1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone

N,n-diethyl-p-phenylenediamine

N,n,n',n'-tetramethyl-p-phenylenediamine

3-methyl-N,N-diethyl-p-phenylenediamine

3-methoxy-N-ethyl-N-ethoxy-p-phenylenediamine, etc.

The non-chromogenic developers in this list are preferred, however,since they avoid any propensity of staining the dye image-receivinglayer.

In a preferred embodiment of the invention, the silver halide developeremployed in the process becomes oxidized upon development and reducessilver halide to silver metal. The oxidized developer thencross-oxidizes the dye-releasing compound. The product ofcross-oxidation then undergoes alkaline hydrolysis, thus releasing animagewise distribution of diffusible azo dye which then diffuses to thereceiving layer to provide the dye image. The diffusible moiety istransferable in alkaline processing composition either by virtue of itsself-diffusivity or by its having attached to it one or moresolubilizing groups, for example, a carboxy, sulpho, sulphonamido,hydroxy or morpholino group.

In using the dye-releasing compounds according to the invention whichproduce diffusible dye images as a function of development, eitherconventional negative-working or direct-positive silver halide emulsionsmay be employed. If the silver halide emulsion employed is adirect-positive silver halide emulsion, such as an internal-imageemulsion designed for use in the internal image reversal process, or afogged, direct-positive emulsion such as a solarizing emulsion, which isdevelopable in unexposed areas, a positive image can be obtained incertain embodiments on the dye image-receiving layer. After exposure ofthe film unit, the alkaline processing composition permeates the variouslayers to initiate development of the exposed photosensitive silverhalide emulsion layers. The developing agent present in the film unitdevelops each of the silver halide emulsion layers in the unexposedareas (since the silver halide emulsions are direct-positive ones), thuscausing the developing agent to become oxidized imagewise correspondingto the unexposed areas of the direct-positive silver halide emulsionlayers. The oxidized developing agent then cross-oxidizes thedye-releasing compounds and the oxidized form of the compounds thenundergoes a base-catalyzed reaction to release the dyes imagewise as afunction of the imagewise exposure of each of the silver halide emulsionlayers. At least a portion of the imagewise distributions of diffusibledyes diffuse to the image-receiving layer to form a positive image ofthe original subject. After being contacted by the alkaline processingcomposition, a pH-lowering layer in the film unit or image-receivingunit lowers the pH of the film unit or image receiver to stabilize theimage.

Internal-image silver halide emulsions useful in this invention aredescribed more fully in the November 1976 edition of ResearchDisclosure, pages 76 through 79, the disclosure of which is herebyincorporated by reference.

The various silver halide emulsion layers of a color film assemblyemployed in this invention can be disposed in the usual order, i.e., theblue-sensitive silver halide emulsion layer first with respect to theexposure side, followed by the green-sensitive and red-sensitive silverhalide emulsion layers. If desired, a yellow dye layer or a yellowcolloidal silver layer can be present between the blue-sensitive andgreen-sensitive silver halide emulsion layers for absorbing or filteringblue radiation that may be transmitted through the blue-sensitive layer.If desired, the selectively sensitized silver halide emulsion layers canbe disposed in a different order, e.g., the blue-sensitive layer firstwith respect to the exposure side, followed by the red-sensitive andgreen-sensitive layers.

The rupturable container employed in certain embodiments of thisinvention can be of the type disclosed in U.S. Pat. Nos. 2,543,181;2,643,886; 2,653,732; 2,723,051; 3,056,492; 3,056,491 and 3,152,515. Ingeneral, such containers comprise a rectangular sheet of fluid- andair-impervious material folded longitudinally upon itself to form twowalls which are sealed to one another along their longitudinal and endmargins to form a cavity in which processing solution is contained.

Generally speaking, except where noted otherwise, the silver halideemulsion layers employed in the invention comprise photosensitive silverhalide dispersed in gelatin and are about 0.6 to 6 microns in thickness;the dye-releasers are dispersed in an aqueous alkalinesolution-permeable polymeric binder, such as gelatin, as a separatelayer about 0.2 to 7 microns in thickness; and the alkalinesolution-permeable polymeric interlayers, e.g., gelatin, are about 0.2to 5 microns in thickness. Of course, these thicknesses are approximateonly and can be modified according to the product desired.

Scavengers for oxidized developing agent can be employed in variousinterlayers of the photographic elements of the invention. Suitablematerials are disclosed on page 83 of the November 1976 edition ofResearch Disclosure, the disclosure of which is hereby incorporated byreference.

Any material can be employed as the image-receiving layer in thisinvention as long as the desired function of mordanting or otherwisefixing the dye image is obtained. The particular material chosen will,of course, depend upon the dye to be mordanted. Suitable materials aredisclosed on pages 80 through 82 of the November 1976 edition ofResearch Disclosure, the disclosure of which is hereby incorporated byreference.

Use of a pH-lowering material in the film units employed in thisinvention will usually increase the stability of the transferred image.Generally, the pH-lowering material will effect a reduction in the pH ofthe image layer from about 13 or 14 to at least 11 and preferably 5 to 8within a short time after imbibition. Suitable materials and theirfunctions are disclosed on pages 22 and 23 of the July 1974 edition ofResearch Disclosure, and pages 35 through 37 of the July 1975 edition ofResearch Disclosure, the disclosures of which are hereby incorporated byreference.

A timing or inert spacer layer can be employed in the practice of thisinvention over the pH-lowering layer which "times" or controls the pHreduction as a function of the rate at which alkali diffuses through theinert spacer layer. Examples of such timing layers and their functionsare disclosed in the Research Disclosure articles mentioned in theparagraph above concerning pH-lowering layers.

The alkaline processing composition employed in this invention is theconventional aqueous solution of an alkaline material, e.g., alkalimetal hydroxides or carbonates such as sodium hydroxide, sodiumcarbonate or an amine such as diethylamine, preferably processing a pHin excess of 11, and preferably containing a developing agent asdescribed previously. Suitable materials and addenda frequently added tosuch compositions are disclosed on pages 79 and 80 of the November 1976edition of Research Disclosure, the disclosure of which is herebyincorporated by reference.

While the alkaline processing composition used in this invention can beemployed in a rupturable container, as described previously, toconveniently facilitate the introduction of processing composition intothe film unit, other methods of inserting processing composition intothe film unit could also be employed, e.g., interjecting processingsolution with communicating members similar to hypodermic syringes whichare attached either to a camera or camera cartridge. The processingcomposition may also be applied by means of a swab or by dipping in abath, if so desired.

The alkaline solution-permeable, substantially opaque, light-reflectivelayer employed in certain embodiments of photographic film units used inthis invention are described more fully in the November 1976 edition ofResearch Disclosure, page 82, the disclosure of which is herebyincorporated by reference.

The supports for the photographic elements used in this invention can beany material as long as it does not deleteriously affect thephotographic properties of the film unit and is dimensionally stable.Typical flexible sheet materials are described on page 85 of theNovember 1976 edition of Research Disclosure, the disclosure of which ishereby incorporated by reference.

While the invention has been described with reference to layers ofsilver halide emulsions and dye image-providing materials, dotwisecoating, such as would be obtained using a gravure printing technique,could also be employed. In this technique, small dots of blue-, green-and red-sensitive emulsions have associated therewith, respectively,dots of yellow, magenta and cyan color-providing substances. Afterdevelopment, the transferred dyes would tend to fuse together into acontinuous tone.

The silver halide emulsions useful in this invention, bothnegative-working and direct-positive ones, are well known to thoseskilled in the art and are described in Product Licensing Index, Volume92, December 1971, publication 9232, page 107, paragraph I, "Emulsiontypes"; they may be chemically and spectrally sensitized as described onpage 107, paragraph III, "Chemical sensitization", and pages 108 and109, paragraph XV, "Spectral sensitization", of the above article; theycan be protected against the production of fog and can be stabilizedagainst loss of sensitivity during keeping by employing the materialsdescribed on page 107, paragraph V, "Antifoggants and stabilizers", ofthe above article; they can contain development modifiers, hardeners,and coating aids as described on pages 107 and 108, paragraph IV,"Development modifiers"; paragraph VII, "Hardeners"; and paragraph XII,"Coating aids", of the above article; they and other layers in thephotographic elements used in this invention can contain plasticizers,vehicles and filter dyes described on page 108, paragraph XI,"Plasticizers and lubricants", and paragraph VIII, "Vehicles", and page109, paragraph XVI, "Absorbing and filter dyes", of the above article;they and other layers in the photographic elements used in thisinvention may contain addenda which are incorporated by using theprocedures described on page 109, paragraph XVII, "Methods of addition",of the above article; and they can be coated by using the varioustechniques described on page 109, paragraph XVIII, "Coating procedures",of the above article, the disclosures of which are hereby incorporatedby reference.

The term "nondiffusing" used herein has the meaning commonly applied tothe term in photography and denotes materials that for all practicalpurposes do not migrate or wander through organic colloid layers, suchas gelatin, in the photographic elements of the invention in an alkalinemedium and preferably when processed in a medium having a pH of 11 orgreater. The same meaning is to be attached to the term "immobile". Theterm "diffusible" as applied to the materials of this invention has theconverse meaning and denotes materials having the property of diffusingeffectively through the colloid layers of the photographic elements inan alkaline medium. "Mobile" has the same meaning as "diffusible".

The term "associated therewith" as used herein is intended to mean thatthe materials can be in either the same or different layers so long asthe materials are accessible to one another.

Example 1 -- Preparation of Compound 1

4-(3-Amino-4-hydroxybenzenesulfonamido)-1-hydroxy-N-[4-(2,4-di-tert-pentylphenoxy)butyl]-2-naphthamidewas diazotized by treating a methanolic solution (150 ml) of itsuccessively with hydrogen chloride (20 ml of 2.25 N, 45 mmol) inmethanol and at 0° C over 5 minutes with 2.7 g (23 mmol) isopentylnitrite. The solution was stirred for 25 minutes at 0° C and added over90 minutes to a slurry containing 3.5 g (22 mmol)3-methyl-4-isoquinolinol [M. M. Robison and B. L. Robison, J. Org.Chem., 21, 1340 (1956)] and 30 g (370 mmol) of sodium acetate in 175 mlmethanol at 0° C. The solid precipitate of maroon dye was filtered off,successively washed with water, dissolved in 200 ml ethyl acetate, andwashed with bicarbonate, dilute hydrochloric acid and water. The ethylacetate solution was dried over anhydrous magnesium sulfate andconcentrated to dryness. The solid was slurried in 400 ml hexane,collected, and vacuum-dried. Yield 12.4 g (75 percent). A solution indimethylacetamide (unmetallized) made alkaline with tetramethylguanidinehad a λ_(max) of 555 nm, ε = 4.7.10⁴.

Intermediate

4-(3-Amino-4-hydroxybenzenesulfonamido)-1-hydroxy-N-[4-(2,4-di-tert-pentylphenoxy)butyl]-2-naphthamide.This compound was prepared in two steps by conventional procedures ofthe type well known in the art.4-Amino-1-hydroxy-N-[4-(2,4-di-tert-pentylphenoxy)butyl]-2-naphthamide(U.S. Pat. No. 3,954,476, column 25) was converted to the sulfonamide byreaction with 4-hydroxy-3-nitrobenzenesulfonyl chloride. Secondly, thenitro group was reduced to the amino compound by catalytichydrogenation.

Example 2 -- Photographic Test - Compound 1

A single-color integral-imaging receiver element was prepared by coatingsuccessively on a polyester film support (1) a metallizing layercomprising gelatin (1.08 g/m²) and nickel sulfate hexahydrate (0.58g/m²), (2) a receiving layer comprising a mixture of gelatin andpoly(4-vinylpyridine), (each at 2.15 g/m²), (3) a reflecting layercomprising titanium dioxide and gelatin in a 6.25/l ratio, (4) an opaquelayer of carbon dispersed in gelatin, (5) a layer comprising gelatin anda dispersion of Compound 1 (illustrated above) (0.84 g/m²), (6) a layerof a red-sensitized internal image emulsion as described in Evans, U.S.Pat. No. 3,761,276 (2.69 g/m² Ag, 2.69 g/m² gelatin), with foggingagents NA-16 and H-25 of Leone et al, U.S. Pat. No. 4,030,925, issuedJune 21, 1977, and 5-octadecylhydroquinone-2-sulfonic acid (16 g/moleAg), (7) a layer of didodecylhydroquinone (1.29 g/m²) dispersed ingelatin (1.61 g/m²), and (8) a gelatin overcoat layer. In a comparativecoating in which no metal ion is used to chelate the dye, the entirelayer 1 was omitted. Layers 1 and 2 above form no part of the invention,as they are the subject of an invention by our coworkers Brust, Hamiltonand Wilkes.

This integral element was exposed to a multicolor test object, thenprocessed by spreading between it and a processing cover sheet, asdescribed in U.S. Pat. No. 4,061,496 of Hannie et al, issued Dec. 6,1977, at 22° C., a viscous processing composition, as described in saidU.S. Pat. No. 4,061,496, by passing the transfer "sandwich" between apair of juxtaposed rollers so that the liquid layer was about 75 μm. Thedye reflection density in the unexposed areas (i.e., D_(max) areas) wasmeasured at selected intervals up to 24 hours with a recordingspectrophotometer. The density at λ_(max) after 4 minutes was determinedfrom the these plots. From the spectrophotometric curves, the finalD_(max), the λ_(max) (i.e., wavelength at D_(max)) and "half band width"(1/2 BW) were determined and recorded in Table I. The "half band width"is the wavelength range at half the D_(max), a measure of purity of hue:The narrower the 1/2 BW, the purer the hue. The light stability wasdetermined by exposing part of the strip to a high intensity daylight(5000 footcandles) light source for two days. Values are given for theoriginal density D_(o), the final faded density D_(F), and the densityloss ΔD.

                  TABLE I                                                         ______________________________________                                        Density at     Hue                                                            Metal-  λ.sub.max After                                                                   λ.sub.max                                                                     1/2 BW Light Stability                              lization                                                                              4 Minutes  (nm)   (nm)   D.sub.o                                                                            D.sub.F                                                                            ΔD                           ______________________________________                                        Ni.sup.++                                                                             1.11       637    127    1.00 0.97 -.03                               None (H)                                                                              1.41       544    186    1.00 0.82 -.18                               ______________________________________                                    

Example 3 -- Spectral Data on Dyes

Table II shows the hue, diffusion, and light stability data for dyeswhich have not been linked to dye-releasing carriers but which have thestructural characteristics of the invention.

Each dye was dissolved at a concentration of 2.5 × 10⁻³ molar in 0.5 Msodium hydroxide solution containing hydroxyethylcellulose (Natrosol250H, 30 g/l) as a thickener. It was spread in a thin layer between acover sheet of polyester film support and a receiving element. When thedye is adsorbed to the mordant, the sheets are peeled apart, and thedyed sheet is washed and dried.

For metallizing with copper (II) ions, the receiving element consistedof a polyester film support and a mordant layer containing a mixture ofgelatin (2.2 g/m²) and a latex,poly(styrene-co-N-benzyl-N,N-dimethyl-N-vinylbenzylammoniumsulfate-co-divinylbenzene) (2.28 g/m²). A sample of the dyed element wastreated for 5 minutes with a solution 0.5 M in cupric ion: 6.0 g cupricnitrate (.3H₂ O), 75 g tartaric acid, 91 ml of potassium dihydrogenphosphate, and sodium hydroxide to adjust the pH to 6.0 (all per literof solution).

For metallizing with nickel (II) ions, the receiving element consistedof a polyester film support coated with Layers 1 and 2 of Example 2.

The washed and dried samples of the metallized receiving elements weresoaked in a phosphate buffer solution at pH 7.0 and again washed anddried. Hue: The wavelength at the maximum density (λ_(max)) of thespectrophotometric curves is recorded in the Table along with the "halfband width" (1/2 BW).

Light Stability: The buffered receiving elements were subjected to 3weeks of a simulated average northern skylight (SANS) (500 footcandles)fading test. The original density D_(o), and the density loss (ΔD) weredetermined from spectrophotometric curves.

                                      TABLE II                                    __________________________________________________________________________    Dyes Unlinked to Carrier                                                       ##STR22##                                                                                                  Chelating                                                                     Metal Ion,                                                                          Hue    Light                                                            Me.sup.++ (or                                                                       λ.sub.max                                                                 1/2 BW                                                                            Stability                          Dye Z            R.sup.8                                                                             G      H.sup.+)                                                                            (nm)                                                                             (nm)                                                                              D.sub.o                                                                           ΔD                       __________________________________________________________________________    A   H            CH.sub.3                                                                            SO.sub.2 NH.sub.2                                                                    Ni    569                                                                               87 1.35                                                                              -0.17                          B   H            CH.sub.3                                                                            COOH   Ni    579                                                                               73 1.33                                                                              -0.11                          C   5-SO.sub.2 NH.sub.2                                                                        CH.sub.3                                                                            OH     Ni    648                                                                              108 1.28                                                                              -0.50                          D   4-SO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            OH     Ni    661                                                                               96 1.13                                                                              -0.36                          E   5-SO.sub.2 CF.sub.3                                                                        CH.sub.3                                                                            OH     Ni    640                                                                              134 0.64                                                                              -0.20                          F   4-NO.sub.2   CH.sub.3                                                                            COOH   Ni    625                                                                              136 1.00                                                                              -0.13                          G   4-NO.sub.2   CH.sub.3                                                                            OH     Ni    708                                                                              150 1.22                                                                              -0.44                          H   H            NH.sub.2                                                                            SO.sub.2 NH.sub.2                                                                    Cu    634                                                                              158 --  --                             I   5-SO.sub.2 NH.sub.2                                                                        NH.sub.2                                                                            OH     Ni    680                                                                              140 --  --                              J**                                                                              4-NO.sub.2   NH.sub.2                                                                            COOH   Ni    655                                                                              101 1.61*                                                                              0.00*                          K**                                                                              H            NH.sub.2                                                                            COOH   Ni    640                                                                              112 1.34*                                                                             -0.01*                         L   H            NHCOCH.sub.3                                                                        NHSO.sub.2 CH.sub.3                                                                  Ni    670                                                                              --  1.90*                                                                             -0.15*                         M   5-SO.sub.2 NH.sub.2                                                                        NHCOCH.sub.3                                                                        OH     Ni    670                                                                              --  1.71*                                                                             -0.12*                              ##STR23##   CH.sub.3                                                                            OH     Ni    648                                                                              --  1.10*                                                                             -0.06*                         O   5-SO.sub.2 NH.sub.2                                                                        OC.sub.2 H.sub.5                                                                    OH     Ni    659                                                                              113 1.02*                                                                             -0.07*                         P   4-SO.sub.2 NH.sub.2                                                                        OC.sub.2 H.sub.5                                                                    OH     Ni    672                                                                              --  0.48*                                                                             -0.03*                         __________________________________________________________________________     *Determined under conditions of Example 2                                     **Coatings were soaked in a 4 percent by weight nickel acetate solution       until no spectrophotometric change could be measured, prior to phosphate      buffer solution treatment.                                               

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be appreciated thatvariations and modifications can be effected within the spirit and scopeof the invention.

What is claimed is:
 1. In a photographic element comprising a supporthaving thereon at least one photosensitive silver halide emulsion layer,said emulsion layer having associated therewith a nondiffusiblecompound, the improvement wherein said nondiffusible compound has atleast one diffusible 1-arylazo-4-isoquinolinol dye moiety, said compoundcontaining:(a) in the ortho position of the arylazo moiety a metalchelating group, a salt thereof or a hydrolyzable precursor thereof; and(b) a ballasted carrier moiety which is capable of releasing saiddiffusible azo dye as a function of development of said silver halideemulsion layer under alkaline conditions.
 2. The photographic element ofclaim 1 wherein said compound has the formula: ##STR24## wherein CARrespresents said ballasted carrier moiety.
 3. The photographic elementof claim 1 wherein said compound has the formula: ##STR25## wherein: Gis a metal chelating group, a salt thereof or a hydrolyzable precursorthereof; a group which together with ##STR26## is CAR, said CAR beingbonded to the benzene ring through the oxygen of said ##STR27## or agroup which together with SO₂ NH is CAR, said CAR being bonded to thebenzene ring through the SO₂ NH group;G¹ is a hydroxy group, a saltthereof, or a hydrolyzable precursor thereof; or a group which togetherwith ##STR28## is CAR, said CAR being bonded to the isoquinoline ringthrough the oxygen of said ##STR29## CAR represents said ballastedcarrier moiety; and t is an integer of 0 or 1, with the proviso that thecompound contains at least one but not more than two CAR groups.
 4. Thephotographic element of claim 3 wherein G¹ is a hydrolyzable precursorof a hydroxy group which comprises an acyloxy group having the formula--OCOR¹, --OCOOR¹, or --OCON(R¹)₂, wherein each R¹ is an alkyl grouphaving 1 to about 8 carbon atoms or an aryl group having 6 to about 12carbon atoms.
 5. The photographic element of claim 3 wherein G ishydroxy; amino, carboxy; sulfonamido; sulfamoyl; a fusednitrogen-containing ring; or a hydrolyzable ester group having theformula --OCOR¹, --OCOOR¹, or --COOR¹, wherein R¹ is an alkyl grouphaving 1 to about 8 carbon atoms or an aryl group having 6 to about 12carbon atoms.
 6. The photographic element of claim 3 wherein CAR is agroup having the formula:

    (Ballast-Carrier-Link) --

wherein: (a) Ballast is an organic ballasting radical of such molecularsize and configuration as to render said compound nondiffusible in saidphotographic element during development in an alkaline processingcomposition; (b) Carrier is an oxidizable acyclic, carbocyclic orheterocyclic moiety; and (c) Link represents a group which, uponoxidation of said carrier moiety, is capable of being hydrolyticallycleaved to release said diffusible azo dye.
 7. The photographic elementof claim 6 wherein the Carrier moiety contains atoms according to thefollowing configuration:

    a (--C═C).sub.b --

wherein: b is a positive integer of 1 to 2; and a represents theradicals OH, SH, NH--, or hydrolyzable precursors thereof.
 8. Thephotographic element of claim 3 wherein CAR is a group having theformula: ##STR30## wherein: (a) Ballast is an organic ballastingradical, of such molecular size and configuration as to render saidcompound nondiffusible in said photographic element during developmentin an alkaline processing composition;(b) D is OR² or NHR³ wherein R² ishydrogen or a hydrolyzable moiety and R³ is hydrogen or a substituted orunsubstituted alkyl group of 1 to 22 carbon atoms; (c) Y represents theatoms necessary to complete a benzene nucleus, a naphthalene nucleus, ora 5 to 7 membered heterocyclic ring; (d) j is a positive integer of 1 to2 and is 2 when D is OR² or NHR³ when R³ is hydrogen or an alkyl groupof less than 8 carbon atoms; and (e) L is a linking group which is[X--(NR⁴ --J)_(q) ]_(m) -- or X--J--NR⁴ -- wherein:(i) X represents abivalent linking group of the formula --R⁵ --L'_(n) --R⁵ _(p) -- whereeach R⁵ can be the same or different and each represents an alkyleneradical having 1 to about 8 carbon atoms; a phenylene radical; or asubstituted phenylene radical having 6 to about 9 carbon atoms; (ii) L'represents a bivalent radical selected from oxy, carbonyl, carboxamido,carbamoyl, sulfonamido, ureylene, sulfamoyl, sulfinyl or sulfonyl; (iii)n is an integer of 0 or 1; (iv) p is 1 when n equals 1 and p is 1 or 0when n equals 0, provided that when p is 1 the carbon content of the sumof both R⁵ radicals does not exceed 14 carbon atoms; (v) R⁴ represents ahydrogen atom, or an alkyl radical having 1 to about 6 carbon atoms;(vi) J represents a bivalent radical selected from sulfonyl or carbonyl;(vii) q represents an integer of 0 or 1; and (viii) m represents aninteger of 0, 1 or
 2. 9. The photographic element of claim 8 wherein Dis OH, j is 2, Y is a naphthalene nucleus, G is OH, G¹ is OH and t is 1.10. The photographic element of claim 1 wherein said diffusible azo dyeis released as an inverse function of said development of said silverhalide emulsion layer under alkaline conditions.
 11. The photographicelement of claim 10 wherein said ballasted carrier moiety is a grouphaving the formula: ##STR31## wherein: Ballast is an organic ballastingradical of such molecular size and configuration as to render saidcompound nondiffusible in said photographic element during developmentin an alkaline processing composition;W¹ represents at least the atomsnecessary to complete a quinone nucleus; r is a positive integer of 1 or2; R⁶ is an alkyl radical having 1 to about 40 carbon atoms or an arylradical having 6 to about 40 carbon atoms; and k is a positive integerof 1 to 2 and is 2 when R⁶ is a radical of less than 8 carbon atoms. 12.The photographic element of claim 10 wherein said ballasted carriermoiety is a group having the formula: ##STR32## wherein: Ballast is anorganic ballasting radical of such molecular size and configuration asto render said compound nondiffusible in said photographic elementduring development in an alkaline processing composition;W² representsat least the atoms necessary to complete a benzene nucleus; and R⁷ is analkyl radical having 1 to about 4 carbon atoms.
 13. The photographicelement of claim 10 wherein said ballasted carrier moiety is a grouphaving the formula: ##STR33## wherein: Ballast is an organic ballastingradical of such molecular size and configuration as to render saidcompound nondiffusible in said photographic element during developmentin an alkaline processing composition;W² represents at least the atomsnecessary to complete a benzene nucleus; and R⁷ is an alkyl radicalhaving 1 to about 4 carbon atoms.
 14. The photographic element of claim10 wherein said ballasted carrier moiety is a group having the formula:##STR34## wherein: Ballast is an organic ballasting radical of suchmolecular size and configuration as to render said compoundnondiffusible in said photographic element during development in analkaline processing composition;W² represents at least the atomsnecessary to complete a benzene nucleus; r is a positive integer of 1 or2; R⁶ is an alkyl radical having 1 to about 40 carbon atoms or an arylradical having 6 to about 40 carbon atoms; k is a positive integer of 1to 2 and is 2 when R⁶ is a radical of less than 8 carbon atoms; and K isOH or a hydrolyzable precursor thereof.
 15. The photographic element ofclaim 1 wherein said dye-releasing compound is: ##STR35##
 16. In aphotographic assemblage comprising:(a) a support having thereon at leastone photosensitive silver halide emulsion layer having associatedtherewith a dye image-providing material; (b) a dye image-receivinglayer; and (c) an alkaline processing composition and means fordischarging same within said assemblage;said assemblage containing asilver halide developing agent, the improvement wherein said dyeimage-providing material is a nondiffusible compound having at least onediffusible 1-arylazo-4-isoquinolinol dye moiety, said compoundcontaining: (a) in the ortho position of the arylazo moiety a metalchelating group, a salt thereof or a hydrolyzable precursor thereof; and(b) a ballasted carrier moiety which is capable of releasing of saidsilver halide emulsion layer under alkaline conditions.
 17. Thephotographic assemblage of claim 16 wherein said compound has theformula: ##STR36## wherein CAR represents said ballasted carrier moiety.18. The photographic assemblage of claim 16 wherein said compound hasthe formula: ##STR37## wherein: G is a metal chelating group, a saltthereof or a hydrolyzable precursor thereof; a group which together with##STR38## is CAR, said CAR being bonded to the benzene ring through theoxygen of said ##STR39## or a group which together with SO₂ NH is CAR,said CAR being bonded to the benzene ring through the SO₂ NH group;G¹ isa hydroxy group, a salt thereof, or a hydrolyzable precursor thereof; ora group which together with ##STR40## is CAR, said CAR being bonded tothe isoquinoline ring through the oxygen of said ##STR41## CARrepresents said ballasted carrier moiety; and t is an integer of 0 or 1,with the proviso that the compound contains at least one but not morethan two CAR groups.
 19. The photographic assemblage of claim 18 whereinG¹ is a hydrolyzable precursor comprising an acyloxy group having theformula --OCOR¹, --OCOOR¹, or --OCON(R¹)₂, wherein each R¹ is an alkylgroup having 1 to about 8 carbon atoms or an aryl group having 6 toabout 12 carbon atoms.
 20. The photographic assemblage of claim 18wherein G is hydroxy; amino; carboxy; sulfonamido; sulfamoyl; a fusednitrogen-containing ring; or a hydrolyzable ester group having theformula --OCOR¹, --OCOOR¹, or --COOR¹, wherein R¹ is an alkyl grouphaving 1 to about 8 carbon atoms or an aryl group having 6 to about 12carbon atoms.
 21. The photograhic assemblage of claim 18 wherein saidCAR is a group having the formula:

    (Ballast-Carrier-Link) --

wherein: (a) ballast is an organic ballasting radical of such molecularsize and configuration as to render said compound nondiffusible in saidphotographic assemblage during development in an alkaline processingcomposition; (b) Carrier is an oxidizable acyclic, carbocyclic orheterocyclic moiety; and (c) Link represents a group which, uponoxidation of said carrier moiety, is capable of said carrier moiety, iscapable of being hydrolytically cleaved to release said diffusible dye.22. The photographic assemblage of claim 21 wherein the Carrier moietycontains atoms according to the following configuration:

    a (--C═C).sub.b --

wherein: b is a positive integer of 1 to 2; and a represents theradicals OH, SH, NH--, or hydrolyzable precursors thereof.
 23. Thephotographic assemblage of claim 16 wherein said dye image-receivinglayer or a layer adjacent thereto contains metal ions.
 24. Thephotographic assemblage of claim 23 wherein:(a) said dye image-receivinglayer is located between said support and said silver halide emulsionlayer; and (b) said assemblage also includes a transparent cover sheetover the layer outermost from said support.
 25. The photographicassemblage of claim 24 wherein said cover sheet has thereon, insequence, a neutralizing layer and a timing layer.
 26. The photographicassemblage of claim 25 wherein said discharging means is a rupturablecontainer containing said alkaline processing composition and anopacifying agent, said container being so positioned during processingof said assemblage that a compressive force applied to said containerwill effect a discharge of the container's contents between saidtransparent sheet and the layer outermost from said support.
 27. Thephotographic assemblage of claim 23 wherein said support having thereonsaid photosensitive silver halide emulsion layer is opaque and said dyeimage-receiving layer is located on a separate transparent supportsuperposed over the layer outermost from said opaque support.
 28. Thephotographic assemblage of claim 27 wherein said transparent support hasthereon, in sequence, a neutralizing layer, a timing layer, and said dyeimage-receiving layer.
 29. In an integral photographic assemblagecomprising:(a) a photosensitive element comprising a transparent supporthaving thereon the following layers in sequence: a dye image-receivinglayer, an alkaline solution-permeable, light-reflective layer, analkaline solution-permeable, opaque layer, a red-sensitive silver halideemulsion layer having a ballasted cyan dye releaser associatedtherewith, a green-sensitive silver halide emulsion layer having aballasted magenta dye releaser associated therewith, and ablue-sensitive silver halide emulsion layer having a ballasted yellowdye releaser associated therewith; (b) a transparent sheet superposedover said blue-sensitive silver halide emulsion layer and comprising atransparent support having thereon, in sequence, a neutralizing layerand a timing layer; and (c) a rupturable container containing analkaline processing composition and an opacifying agent which is sopositioned during processing of said assemblage that a compressive forceapplied to said container will effect a discharge of the container'scontents between said transparent sheet and said blue-sensitive silverhalide emulsion layer; said assemblage containing a silver halidedeveloping agent; the improvement wherein at least one of said ballasteddye releasers is a nondiffusible compound having at least one diffusible1-arylazo-4-isoquinolinol dye moiety, said compound containing: (a) inthe ortho position of the arylazo moiety a metal chelating group, a saltthereof or a hydrolyzable precursor thereof; and (b) a ballasted carriermoiety which is capable of releasing said diffusible azo dye as afunction of development of said silver halide emulsion layer underalkaline conditions.
 30. The photographic assemblage of claim 29 whereinsaid compound has the formula: ##STR42## wherein: G is a metal chelatinggroup, a salt thereof or a hydrolyzable precursor thereof; a group whichtogether with ##STR43## is CAR, said CAR being bonded to the benzenering through the oxygen of said ##STR44## or a group which together withSO₂ NH is CAR, said CAR being bonded to the benzene ring through the SO₂NH group;G¹ is a hydroxy group, a salt thereof, or a hydrolyzableprecursor thereof; or a group which together with ##STR45## is CAR, saidCAR being bonded to the isoquinoline ring through the oxygen of said##STR46## CAR represents said ballasted carrier moiety; and t is aninteger of 0 or 1, with the proviso that the compound contains at leastone but not more than two CAR groups.
 31. The photographic assemblage ofclaim 29 wherein said dye image-receiving layer or a layer adjacentthereto contains metal ions.
 32. A process for producing a photographictransfer image in color in an imagewise-exposed photographic elementcomprising a support having thereon at least one photosensitive silverhalide emulsion layer, said emulsion layer having associated therewith anondiffusible compound having at least one diffusible1-arylazo-4-isoquinolinol dye moiety, said compound containing:(A) inthe ortho position of the arylazo moiety a metal chelating group, a saltthereof or a hydrolyzable precursor thereof; and (B) a ballasted carriermoiety which is capable of releasing said diffusible azo dye as afunction of development of said silver halide emulsion layer underalkaline conditions, said process comprising:(1) treating said elementwith an alkaline processing composition in the presence of a silverhalide developing agent to effect development of each of the exposedsilver halide emulsion layers; (2) said dye-releasing compound thenreleasing said diffusible azo dye imagewise as a function of saiddevelopment of each of said silver halide emulsion layers; (3) at leasta portion of said imagewise distribution of said azo dye diffusing to adye image-receiving layer; and (d) contacting said imagewisedistribution of said azo dye in said dye image-receiving layer withmetal ions, thereby forming a metal-complexed azo dye transfer image.33. The process of claim 32 wherein said non-diffusible compound has theformula: ##STR47## wherein: G is a metal chelating group, a salt thereofor a hydrolyzable precursor thereof; a group which together with##STR48## is CAR, said CAR being bonded to the benzene ring through theoxygen of said ##STR49## or a group which together with SO₂ NH is CAR,said CAR being bonded to the benzene ring through the SO₂ NH group;G¹ isa hydroxy group, a salt thereof, or a hydrolyzable precursor thereof; ora group which together with ##STR50## is CAR, said CAR being bonded tothe isoquinoline ring through the oxygen of said ##STR51## CARrepresents said ballasted carrier moiety; and t is an integer of 0 or 1,with the proviso that the compound contains at least one but not morethan two CAR groups.
 34. A process for producing a photographic transferimage in color in an imagewise-exposed photographic element comprising asupport having thereon at least one photosensitive silver halideemulsion layer, said emulsion layer having associated therewith anondiffusible compound having at least one diffusible1-arylazo-4-isoquinolinol dye moiety, said compound containing:(A) inthe ortho position of the arylazo moiety metal chelating group, a saltthereof or a hydrolyzable precursor thereof; and (B) a ballasted carriermoiety which is capable of releasing said diffusible azo dye as afunction of development of said silver halide emulsion layer underalkaline conditions, said ballasted carrier moiety being a group havingthe formula: ##STR52## wherein: (a) Ballast is an organic ballastingradical of such molecular size and configuration as to render saidcompound nondiffusible in said photographic element during developmentin an alkaline processing composition; (b) D is OR² or NHR³ wherein R²is hydrogen or a hydrolyzable moiety and R³ is hydrogen or a substitutedor unsubstituted alkyl group of 1 to 22 carbon atoms; (c) Y representsthe atoms necessary to complete a benzene nucleus, a naphthalenenucleus, or a 5 to 7 membered heterocyclic ring; (d) j is a positiveinteger of 1 to 2 and is 2 when D is OR² or NHR³ when R³ is hydrogen oran alkyl group of less than 8 carbon atoms; and (e) L is a linking groupwhich is [X--(NR⁴ --J)_(q) ]_(m) -- or X--J--NR⁴ -- wherein:(i) Xrepresents a bivalent linking group of the formula --R⁵ --L'_(n) --R⁵_(p) -- where each R⁵ can be the same or different and each representsan alkylene radical having 1 to about 8 carbon atoms; a phenyleneradical; or a substituted phenylene radical having 6 to about 9 carbonatoms; (ii) L' represents a bivalent radical selected from oxy,carbonyl, carboxamido, carbamoyl, sulfonamido, ureylene, sulfamoyl,sulfinyl or sulfonyl; (iii) n is an integer of 0 or 1; (iv) p is 1 whenn equals 1 and p is 1 or 0 when n equals 0, provided that when p is 1the carbon content of the sum of both R⁵ radicals does not exceed 14carbon atoms; (v) R⁴ represents a hydrogen atom, or an alkyl radicalhaving 1 to about 6 carbon atoms; (vi) J represents a bivalent radicalselected from sulfonyl or carbonyl; (vii) q represents an integer of 0to 1; and (viii) m represents an integer of 0, 1 or 2,said processcomprising: (1) treating said photographic element with an alkalineprocessing composition in the presence of a silver halide developingagent to effect development of each of the exposed silver halideemulsion layers, thereby oxidizing said developing agent; (2) saidoxidized developing agent thereby cross-oxidizing said dye-releasingcompound; (3) said cross-oxidized dye-releasing compound then cleavingas a result of alkaline hydrolysis to release said diffusible azo dyeimagewise as a function of said imagewise exposure of each of saidsilver halide emulsion layers; (4) at least a portion of said imagewisedistribution of said azo dye diffusing to a dye image-receiving layer;and (5) contacting said imagewise distribution of said azo dye withmetal ions, thereby forming a metal-complexed azo dye transfer image.35. The process of claim 34 wherein D is OH, j is 2, Y is a naphthalenenucleus, G is OH, G¹ is OH and t is 1.